Synthesis of core-shell nanostructured Cr2O3/C@TiO2 for photocatalytic hydrogen production

In this study,the Cr2O3/C@TiO2 composite was synthesized via the calcination of yolk–shell MIL-101@TiO2.The composite presented core–shell structure,where Cr-doped TiO2 and Cr2O3/C were the shell and core,respectively.The introduction of Cr^3+and Cr2O3/C,which were derived from the calcination of MIL-101,in the composite enhanced its visible light absorbing ability and lowered the recombination rate of the photogenerated electrons and holes.The large surface area of the Cr2O3/C@TiO2 composite provided numerous active sites for the photoreduction reaction.Consequently,the photocatalytic performance of the composite for the production of H2 was better than that of pure TiO2.Under the irradiation of a 300 W Xe arc lamp,the H2 production rate of the Cr2O3/C@TiO2 composite that was calcined at 500°C was 446μmol h−1 g−1,which was approximately four times higher than that of pristine TiO2 nanoparticles.Moreover,the composite exhibited the high H2 production rate of 25.5μmol h−1 g−1 under visible light irradiation(λ>420 nm).The high photocatalytic performance of Cr2O3/C@TiO2 could be attributed to its wide visible light photoresponse range and efficient separation of photogenerated electrons and holes.This paper offers some insights into the design of a novel efficient photocatalyst for water-splitting applications.

Immobilization of metalloporphyrins on CeO_2@SiO_2 with a core-shell structure prepared via microemulsion method for catalytic oxidation of ethylbenzene

Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin catalysts were characterized by N2 adsorption-desorption isotherm(BET), scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), ultraviolet and visible spectroscopy(UV-Vis), and Fourier transform infrared spectroscopy(FT-IR). The results show that the morphology of Ce O2@Si O2 nanoparticles is core-shell microspheres with about 30 nm in diameter, and metalloporphyrins are immobilized on the Ce O2@Si O2 core-shell nanoparticles via amide bond. Especially, the core-shell structure contains multi Ce O2 core and thin Si O2 shell, which may benefit the synergistic effect between the Ce O2 core and the porphyrin anchored on the very thin Si O2 shell. As a result, this supported metalloporphyrin catalysts present comparably high catalytic activity and stability for oxidation of ethylbenzene with molecular oxygen, namely, ethylbenzene conversion remains around 12% with identical selectivity of about 80% for acetophenone even after six-times reuse of the catalyst.

Mitigating Lattice Distortion of High‑Voltage LiCoO_(2)via Core‑Shell Structure Induced by Cationic Heterogeneous Co‑Doping for Lithium‑Ion Batteries

Inactive elemental doping is commonly used to improve the structural stability of high-voltage layered transition-metal oxide cathodes.However,the one-step co-doping strategy usually results in small grain size since the low diffusivity ions such as Ti^(4+)will be concentrated on grain boundaries,which hinders the grain growth.In order to synthesize large single-crystal layered oxide cathodes,considering the different diffusivities of different dopant ions,we propose a simple two-step multi-element co-doping strategy to fabricate core–shell structured LiCoO_(2)(CS-LCO).In the current work,the high-diffusivity Al^(3+)/Mg^(2+)ions occupy the core of single-crystal grain while the low diffusivity Ti^(4+)ions enrich the shell layer.The Ti^(4+)-enriched shell layer(~12 nm)with Co/Ti substitution and stronger Ti–O bond gives rise to less oxygen ligand holes.In-situ XRD demonstrates the constrained contraction of c-axis lattice parameter and mitigated structural distortion.Under a high upper cut-off voltage of 4.6 V,the single-crystal CS-LCO maintains a reversible capacity of 159.8 mAh g^(−1)with a good retention of~89%after 300 cycles,and reaches a high specific capacity of 163.8 mAh g^(−1)at 5C.The proposed strategy can be extended to other pairs of low-(Zr^(4+),Ta^(5+),and W6+,etc.)and high-diffusivity cations(Zn^(2+),Ni^(2+),and Fe^(3+),etc.)for rational design of advanced layered oxide core–shell structured cathodes for lithium-ion batteries.

Construction of MoP/MoS_(2) Core-shell Structure Electrocatalyst for Boosting Hydrogen Evolution Reaction

Hydrogen energy stands out as one of the most promising alternative energy sources due to its cleanliness and renewability.Electrocatalytic water splitting offers a sustainable pathway for hydrogen production.However,the kinetic rate of the hydrogen evolution reaction(HER)is sluggish,emphasizing the critical need for stable and highly active electrocatalysts to facilitate HER and enhance reaction efficiency.Transition metal-based catalysts have garnered attention for their favorable catalytic activity in electrochemical hydrogen evolution in alkaline electrolytes.In this investigation,flower-like nanorods of MoS_(2) were directly synthesized in situ on a nickel foam substrate,followed by the formation of MoP/MoS_(2)-nickel foam(NF)heterostructures through high-temperature phosphating in a tube furnace environment.The findings reveal that MoP/MoS_(2)-NF-450 exhibits outstanding electrocatalytic performance in an alkaline milieu,demonstrating a low overpotential(90 mV)and remarkable durability at a current density of 10 mA/cm^(2).Comprehensive analysis indicates that the introduction of phosphorus(P)atoms enhances the synergistic effect with MoS_(2),while the distinctive flower-like nanorod structure of MoS_(2) exposes more active sites.Moreover,the interface between the MoP/MoS_(2) heterostructure and NF facilitates electron transfer during hydrogen evolution,thereby enhancing electrocatalytic performance.The design and synthesis of such catalysts offer a valuable approach for the development of high-performance hydrogen evolution electrocatalysts.

Sulfide@hydroxide core–shell nanostructure via a facile heating-electrodeposition method for enhanced electrochemical and photoelectrochemical water oxidation

Designing low-cost,easy-fabricated,highly stable and active electrocatalysts for oxygen evolution reaction(OER) is crucial for electrochemical(EC) and solar-driven photoelectrochemical(PEC) water splitting.By using a facile heating-electrodeposition method,here we fabricated a porous but crystalline Fe-doped Ni3 S2.A thin porous surface NiFe hydroxide layer(~10 nm) is then formed through OER-running.By virtue of the core Fe-doped Ni3 S2 with good conductivity and the shell NiFe hydroxide surface with good electrocatalytic activity,the core-shell nanostructure on Ni foam exhibits excellent OER activity in 1 M NaOH,needing only 195 and 230 mV to deliver 10 and 100 mA/cm^(2),respectively,much more superior to those of 216 and 259 mV for the sample deposited under normal temperature.The enhanced photo-response of the sulfide@hydroxide core-shell structure was also demonstrated,due to the efficient transfer of photo-generated carriers on the core/shell interface.More interestingly,it shows a good compatibility with Si based photoanode,which exhibits an excellent PEC performance with an onset potential of 0.86 V vs.reversible hydrogen electrode,an applied bias photon-to-current efficiency of 5.5% and a durability for over 120 h under AM 1.5 G 1 sun illumination,outperforming the state-of-the-art Si based photoanodes.

Core-shell structured Co@NC@MoS_(2)magnetic hierarchical nanotubes:Preparation and microwave absorbing properties

In this study,a new lightweight one-dimensional absorber Co@NC@MoS_(2)was designed and prepared.Firstly,polydopamine(PDA)was coated by oxidative self-polymerization with cobalt-nitrilotriacetic acid chelate nanowires(Co-NTAC)as template.Then core-shell structured magnetic hierarchical nanotubes(Co@PDA@MoS_(2))were prepared by one-step hydrothermal method.After thermal annealing,PDA layer was transformed into nitrogen doped carbon layer(NC)to obtain the efficient microwave absorber Co@NC@MoS_(2).The removal of template and growth of MoS_(2)were completed simultaneously,the preparation process was simplified.Because of its good magnetic loss and dielectric loss,Co@NC@MoS_(2)shows excellent microwave absorption performance.Under filler content of 15 wt.%,the minimum reflection loss(RL_(min))can reach-61.97 dB@9.2 GHz,and the effective absorption bandwidth(EAB)is 5.6 GHz.The electromagnetic parameters of Co@NC@MoS_(2)can be further adjusted by changing the load of MoS_(2).Meanwhile,the structure and composition of Co@NC@MoS_(2)were systematically analyzed.The influence of the microstructure on the microwave absorbing properties was investigated,and the microwave attenuation mechanism is revealed.As an efficient and lightweight absorber,Co@NC@MoS_(2)has potential application value in the construction of new stealth coatings.

Preparation and characterization of monodispersed spherical Fe_2O_3@SiO_2 reddish pigments with core-shell structure

The α-Fe_2 O_3@SiO_2 reddish pigments with core-shell structure were successfully prepared by hydrothermal and Stober methods. The structure, morphology, and chromaticity of the synthesized pigments were characterized by XRD, SEM, TEM, FTIR, XPS, and colorimetry. The results indicated that the as-prepared pigments have the characteristics of narrow particle size distribution, high dispersion,and good sphericity. The α-Fe_2 O_3@SiO_2 reddish pigments were uniform and well dispersed in solution. In addition, the pigments with different shell thickness were also prepared, and the effect of shell thickness on the color performance of the pigments was discussed.

Synthesis of core-shell structured Au@Bi2S3 nanorod and its application as DNA immobilization matrix for electrochemical biosensor construction

The core-shell structured Au@Bi2S3 nanorods have been prepared through direct in-situ growth of Bi2S3 at the surface of pre-synthesized gold nanorods.The product was characterized by X-ray diffraction,transmission electron microscopy and energy-dispersive X-ray spectroscopy.Then the obtained Au@Bi2S3 nanorods were coated onto glassy carbon electrode to act as a scaffold for fabrication of electrochemical DNA biosensor on the basis of the coordination of-NH2 modified on 5’-end of probe DNA and Au@Bi2S3.Electrochemical characterization assays demonstrate that the Au@Bi2S3 nanorods behave as an excellent electronic transport channel to promote the electron transfer kinetics and increase the effective surface area by their nanosize effect.The hybridization experiments reveal that the Au@Bi2S3 matrix-based DNA biosensor is capable of recognizing complementary DNA over a wide concentration ranging from 10 fmol/L to 1 nmol/L.The limit of detection was estimated to be 2 fmol/L(S/N=3).The biosensor also presents remarkable selectivity to distinguish fully complementa ry sequences from basemismatched and non-complementary ones,showing great promising in practical application.

Property-performance relationship of core-shell structured black TiO_(2) photocatalyst for environmental remediation

Understanding the relationship between the properties and performance of black titanium dioxide with core-shell structure(CSBT)for environmental remediation is crucial for improving its prospects in practical applications.In this study,CSBT was synthesized using a glycerol-assisted sol-gel approach.The effect of different water-to-glycerol ratios(W:G=1:0,9:1,2:1,and 1:1)on the semiconducting and physicochemical properties of CSBT was investigated.The effectiveness of CSBT in removing phenolic compounds(PHCs)from real agro-industrial wastewater was studied.The CSBT synthesized with a W:G ratio of 9:1 has optimized properties for enhanced removal of PHCs.It has a distinct coreshell structure and an appropriate amount of Ti3+cations(11.18%),which play a crucial role in enhancing the performance of CSBT.When exposed to visible light,the CSBT performed better:48.30%of PHCs were removed after 180 min,compared to only 21.95%for TiO_(2) without core-shell structure.The CSBT consumed only 45.5235 kWh/m^(3) of electrical energy per order of magnitude and cost$2.4127 per unit volume of treated agro-industrial wastewater.Under the conditions tested,the CSBT demonstrated exceptional stability and reusability.The CSBT showed promising results in the treatment of phenols-containing agro-industrial wastewater.

Tracking the atomic pathways of Pt3Ni-Ni(OH)2 core-shell structures at the gas-liquid interface by in-situ liquid cell TEM

Using the in-situ liquid cell transmission electron microscopy, the three-stage growth of Pt3Ni-Ni(OH)2 core-shell structures at the gas-liquid interfaces was clearly observed, which consists of(1) a thermodynamically driven Pt3Ni alloy core by the monomer attachment,(2) a nickel(Ni) shell formation due to the depletion of the Pt salt precursor, and(3) the oxidation and of the Ni shell into Ni(OH)2 flakes. We also further observed the nucleation and growth of the Ni(OH)2 flakes on an existing layer either at the middle part or at the step edge. More interestingly, the dynamic transformation among a Pt3Ni alloy, Ni clusters and Ni(OH)2 flakes was also imaged even at a high electron dose rate.

Mechanical properties of individual core-shell-structured Sn O2@C nanofibers investigated by atomic force microscopy and finite element method

Although SnO_2-based nanomaterials used to be considered as being extraordinarily versatile for application to nanosensors,microelectronic devices, lithium-ion batteries, supercapacitors and other devices, the functionalities of SnO_2-based nanomaterials are severely limited by their intrinsic vulnerabilities. Facile electrospinning was used to prepare SnO_2 nanofibers coated with a protective carbon layer. The mechanical properties of individual core-shell-structured SnO_2@C nanofibers were investigated by atomic force microscopy and the finite element method. The elastic moduli of the carbon-coated SnO_2 nanofibers remarkably increased, suggesting that coating SnO_2 nanofibers with carbon could be an effective method of improving their mechanical properties.

Magnetic NiFe_(2)O_(4)@FeNi_(3)core-shell nanospheres derived from FeNi-LDH precursor anchoring on rGO nanosheets for enhanced electromagnetic wave absorption

Graphene has been extensively utilized in the domain of electromagnetic wave(EMW)absorption ma-terials because of its excellent electrical conductivity.However,the inferior impedance matching per-formance and the single loss mechanism vastly restrict the application.Hence,it’s an effective strat-egy to solve these issues by introducing magnetic components.Notably,layer double hydroxide(LDH)is an appropriate template to obtain magnetic component materials.Considering that ferromagnetic met-als such as Fe,Co,Ni,and their corresponding metal oxides are usually treated as magnetic compo-nents which are promising candidates for EMW absorption materials.Therefore,in this work,a FeNi-layered double hydroxide-reduced graphene oxide(FeNi-LDH-rGO)aerogel was synthesized through a series of processes such as electrostatic self-assembly,hydrothermal,freeze-drying,and annealing.The magnetic NiFe_(2)O_(4)@FeNi_(3)core-shell nanospheres were obtained from FeNi-LDH precursor,anchoring on rGO nanosheets after the annealing treatment.Furthermore,the effects of different mass ratios of LDH to GO as well as different annealing temperatures of LDH-rGO aerogel on the EMW absorption prop-erty and impedance matching performance were explored.As a consequence,the fabricated ultralight 600LDH-rGO 2:1 aerogel shows a broad effective absorption bandwidth(EAB)of 7.04 GHz at a thickness of 2.3 mm with a low filling content of only 6 wt%and a low density of 4.4 mg/cm^(3).In conclusion,the synthetic LDH-rGO aerogels offer an effective strategy for preparing EMW absorption materials that own three-dimensional porous network structure and unique magnetic NiFe_(2)O_(4)@FeNi_(3)core-shell struc-ture nanospheres.

One-pot hydrothermal synthesis of willow branch-shaped MoS_2/CdS heterojunctions for photocatalytic H_2 production under visible light irradiation

Willow branch-shaped MoS2/CdS heterojunctions are successfully synthesized for the first time by a facile one-pot hydrothermal method. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, diffuse reflectance spectroscopy, and photoelectrochemical and photoluminescence spectroscopy tests. The photocatalytic hydrogen evolution activities of the samples were evaluated under visible light irradiation. The resulting MoS2/CdS heterojunctions exhibit a much improved photocatalytic hydrogen evolution activity than that obtained with CdS and MoS2. In particular, the optimized MC-5 (5 at.% MoS2/CdS) photocatalyst achieved the highest hydrogen production rate of 250.8 μmol h–1, which is 28 times higher than that of pristine CdS. The apparent quantum efficiency (AQE) at 420 nm was 3.66%. Further detailed characterizations revealed that the enhanced photocatalytic activity of the MoS2/CdS heterojunctions could be attributed to the efficient transfer and separation of photogenerated charge carriers resulting from the core-shell structure and the close contact between MoS2 nanosheets and CdS single-crystal nanorods, as well as to increased visible light absorption. A tentative mechanism for photocatalytic H2 evolution by MoS2/CdS heterojunctions was proposed. This work will open up new opportunities for developing more efficient photocatalysts for water splitting.

ZrO2/PMMA Nanocomposites： Preparation and Its Dispersion in Polymer Matrix

ZrO2/PMMA nanocomposite particles are synthesized through an in-situ free radical emulsion polymerization based on the silane coupling agent （Z-6030） modified ZrO2 nanoparticles, and the morphology, size and its distribution of nanocomposite particles are investigated. Scanning electron microscopy （SEM） images demonstrate that the methyl methacrylate （MMA） feeding rate has a significant effect on the particle size and morphology. When the MMA feeding rate decreases from 0.42 ml-min-1 to 0.08 ml. min-1, large particles （about 200-550.nm） will not form, and the size distribution become narrow （36-54 nm）. The average nanocomposite particles size increases from 34 nm to 55 nm, as the MMA/ZrO2 nanoparticles mass ratio increased from 4 ： 1 to 16 ： 1. Regular spherical ZrO2/PMMA nanocomposite particles are synthesized when the emulsifier OP-10 concentration is 2 mg.m1-1. The nanocomposite particles could be mixed with VAc-VeoVa10 polymer matrix just by magnetic stirring to prepare the ZrOE/PMMA/VAc-VeoVal0 hybrid coatings. SEM and atomic force microscopy （AFM） photos reveal that the distribution of the ZrO2/PMMA nanocomposite particles in the VAc-VeoVal0 polymer matrix is homogenous and stable. Here, the grafted-PMMA polymer on ZrO2 nanoparticles plays as a bridge which effectively connects the ZrO2 nanoparticles and the VAc-VeoVal0 polymer matrix with improved comparability. In consequence, the hybrid coating with good dispersion stability is obtained.

Atomic Modulation of 3D Conductive Frameworks Boost Performance of MnO2 for Coaxial Fiber‑Shaped Supercapacitors

Coaxial fiber-shaped supercapacitors are a promising class of energy storage devices requiring high performance for flexible and miniature electronic devices.Yet,they are still struggling from inferior energy density,which comes from the limited choices in materials and structure used.Here,Zn-doped CuO nanowires were designed as 3D framework for aligned distributing high mass loading of MnO2 nanosheets.Zn could be introduced into the CuO crystal lattice to tune the covalency character and thus improve charge transport.The Zn–CuO@MnO2 as positive electrode obtained superior performance without sacrificing its areal and gravimetric capacitances with the increasing of mass loading of MnO2 due to 3D Zn–CuO framework enabling efficient electron transport.A novel category of free-standing asymmetric coaxial fiber-shaped supercapacitor based on Zn0.11CuO@MnO2 core electrode possesses superior specific capacitance and enhanced cell potential window.This asymmetric coaxial structure provides superior performance including higher capacity and better stability under deformation because of sufficient contact between the electrodes and electrolyte.Based on these advantages,the as-prepared asymmetric coaxial fiber-shaped supercapacitor exhibits a high specific capacitance of 296.6 mF cm^−2 and energy density of 133.47μWh cm^−2.In addition,its capacitance retention reaches 76.57%after bending 10,000 times,which demonstrates as-prepared device’s excellent flexibility and long-term cycling stability.

Optimization of core-shell structure distribution in sintered Nd-Fe-B magnets by titanium addition

In view of the uneven distribution of the core-shell structure of sintered Nd-Fe-B magnets after grain boundary diffusion,this study proposes to use high-melting-point and reactive element titanium(Ti)as an additive to increase the diffusion channels and to enhance the diffusion of heavy rare earth elements along the grain boundary phase.By adding Ti element,the diffusion depth and hence the intrinsic coercivity of magnets are increased significantly.The addition of Ti increases the coercivity at two stages:initially from 16.07 to 16.29 kOe by addition effect,and then from 16.29 to 25.16 kOe by facilitating the diffusion of Tb element.The formation of TiB_(2) phase improves the periodic arrangement of the crystal structure in the surroundings of the grain boundary phase and enhances its activity.The improved grain boundary diffusion and better core-shell structure distribution provide a theoretical guidance fo r solving the problem of diffusion depth in bulk magnets.

A core–shell Ni/SiO_(2)@TiO_(2) catalyst for highly selective one-step synthesis of 2-propylheptanol from n-pentanal

One-step synthesis of 2-propylheptanol(2-PH)from n-pentanal via a reaction integration of n-pentanal self-condensation and successive hydrogenation is of great significance for it can simplify process flow and reduce energy consumption.The key to promotion of 2-PH selectivity is to enhance the competitiveness of n-pentanal self-condensation with respect to its direct hydrogenation.For this purpose,a core–shell structured Ni/SiO_(2)@TiO_(2) catalyst was designed and prepared.With the precise architecture of this core–shell structured catalyst,n-pentanal can be firstly in contact with TiO_(2) to 2-propyl-2-heptenal(2-PHEA)while the direct hydrogenation to n-pentanol can be effectively inhibited,and then 2-PHEA diffuses into the core of Ni/SiO_(2) and is hydrogenated to 2-PH.The spatial threshold of the core–shell catalyst significantly enhanced its catalytic performance;a 2-PH selectivity of 77.9%was reached with a 100%npentanal conversion.The 2-PH selectivity is much higher than that obtained by employing Ni/TiO_(2) catalyst.Furthermore,the reaction kinetics of one-step synthesis of 2-PH from n-pentanal catalyzed by Ni/SiO_(2)@TiO_(2) was studied and its kinetic model was established which is useful for reactor design and scale-up.

Surface modification of Cu_(2)O with stabilized Cu^(+) for highly efficient and stable CO_(2) electroreduction to C_(2+) chemicals

Copper(Cu)-based materials are known as the most attractive catalysts for electrochemical carbon dioxide reduction reaction(CO_(2)RR),especially the Cu^(+) species(e.g.,Cu_(2)O),which show excellent capability for catalyzing CO_(2) to C_(2+) chemicals because of their unique electronic structure.However,the active Cu^(+) species are prone to be reduced to metallic Cu under an electroreduction environment,thus resulting in fast deactivation and poor selectivity.Here,we developed an advanced surface modification strategy to maintain the active Cu^(+) species via assembling a protective layer of metal-organic framework(copper benzenetricarboxylate,CuBTC) on the surface of Cu_(2)O octahedron(Cu_(2)O@CuBTC).It's encouraging to see that the Cu_(2)O@CuBTC heterostructure outperforms the bare Cu_(2)O octahedron in catalyzing CO_(2) to C_(2+) chemicals and dramatically enhances the ratio of C_(2)H_(4)/CH_(4) products.A systematic study reveals that the introduced CuBTC shell plays a critical role in maintaining the active Cu^(+) species in Cu_(2)O@CuBTC heterostructure under reductive conditions.This work offers a practical strategy for improving the catalytic performance of CO_(2)RR over copper oxides and also establishes a route to maintain the state of valence-sensitive catalysts.

PREPARATION OF POLYSTYRENE/SiO_2 COMPOSITE NANOPARTICLES BEARING SULFONIC GROUPS ON THE SURFACE VIA EMULSION COPOLYMERIZATION USING A POLYMERIZABLE EMULSIFIER

Functionalized PS/SiO_2 composite nanoparticles bearing sulfonic groups on the surface were successfully synthesized via emulsion copolymerization using a polymerizable emulsifierαolefin solfonate(AOS).As demonstrated by transmission electron microscopy and atomic force microscopy,well-defined core-shell PS/SiO_2 composite nanoparticles with a diameter of 50 nm were obtained.Sulfonic groups introduced onto the surface of the composite nanoparticles were quantified by FTIR,and can be controlled to some exten...

Ternary core-shell structured transition metal chalcogenide for hybrid electrochemical capacitor

Hybrid structured semiconductor nanomaterials possess excellent electrochemical performances owing to the synergistic effects from two components. Herein we report a novel CoMo;S;@Zn-Co-S core-shell structure as the electrode materials for asymmetric supercapacitor. The unique electrode structure is beneficial to rapid electron transport and the ion diffusion due to the existence of many vast channels.The as-synthesized core-shell structured electrode exhibits an overall improved electrochemical performance. Moreover, a quasi-solid state asymmetric supercapacitor is fabricated. It reveals a specific capacitance of 0.84 C/cm;collected at 4mA/cm;and an energy density of 1.87 mWh/cm;at a power density of 31.99 W/cm;.